US2319976A - Dehydroabietinal and method of producing - Google Patents
Dehydroabietinal and method of producing Download PDFInfo
- Publication number
- US2319976A US2319976A US454457A US45445742A US2319976A US 2319976 A US2319976 A US 2319976A US 454457 A US454457 A US 454457A US 45445742 A US45445742 A US 45445742A US 2319976 A US2319976 A US 2319976A
- Authority
- US
- United States
- Prior art keywords
- acid
- dehydroabietinal
- hydrogen
- producing
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- YCLCHPWRGSDZKL-UHFFFAOYSA-N Dehydro-abietinal Natural products O=CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 YCLCHPWRGSDZKL-UHFFFAOYSA-N 0.000 title description 12
- YCLCHPWRGSDZKL-SLFFLAALSA-N dehydroabietadienal Chemical compound O=C[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 YCLCHPWRGSDZKL-SLFFLAALSA-N 0.000 title description 12
- 238000000034 method Methods 0.000 title description 10
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical class OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 12
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 11
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 229940118781 dehydroabietic acid Drugs 0.000 description 11
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000007659 semicarbazones Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UJTTUOLQLCQZEA-UHFFFAOYSA-N 9h-fluoren-9-ylmethyl n-(4-hydroxybutyl)carbamate Chemical compound C1=CC=C2C(COC(=O)NCCCCO)C3=CC=CC=C3C2=C1 UJTTUOLQLCQZEA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
Definitions
- This invention relates to a new composition of matter and .to a method for its production. More particularly, it relates to dehydroabietinal as a new composition of matter and to a method of production thereof.
- dehydroabietic acid Several derivatives of dehydroabietic acid have been described in the art. However, the aldehyde containing the hydrocarbon nucleus of dehydroabietic acid but having the carboxyl group replaced by the aldehyde group has not been prepared or described previously.
- dehydroabietinal the aldehyde corresponding to dehydroabietic acid with substitution of the carboxyl group by the aldehyde group
- Its method of preparation involves reduction of the acid halide such as the acid chloride or acid bromide formed from. dehydroabietic acid.
- Dehydroabietinal is believed to have the following structural formula:
- the solution was then cooled and the reaction vessel flushed out with nitrogen.
- the reaction solution was then filtered to separate the catalyst and the filtrate steam-distilled, leaving the dehydroabietinal behind as a viscous liquid.
- the dehydroabietinal was converted to its semicarbazone by dissolving in methyl alcohol and adding 'suflicient semicarbazide hydrochloride and 12 parts of sodium bicarbonate dissolved in methanol.
- the solution of the semicarbazone resulting was concentrated and cooled to precipitate the semicarbazone.
- the first crop of crystals obtained amounted to 8.3 parts by weight and a second crop amounted to 38% of the theoretical.
- the melting point of the crystalline semicarbazone was 217 to 219 C.
- While the above example illustrates the reduction of the acid chloride of dehydroabietic acid by means of a catalyst comprising palladium on barium sulfate, other catalysts for carrying out the reduction may also be used such as other noble metal hydrogenation catalysts.
- the catalyst employed must be sufficiently active to facilitate the replacement of the halogen of the acid halide by hydrogen but not so active as to further reduce the aldehyde group formed. Palladium supported on an inert base such as barium sulfate is particularly desirable.
- a solution of the acid halide such as the acid chloride or acid bromide of dehydroabietic acid in a suitable solvent such as benzene, toluene, xylene, or purified petroleum fractions will be employed.
- the temperature for carrying out the reduction may be varied to provide suitable reaction but preferably will be within the range of about 80 to about C. The time required for carrying out the reaction will be dependent on the particular catalyst used as well as on the particular temperature used.
- the acid chloride of dehydroabietic acid useful in the production of dehydroabietinal in accordance with this invention may be obtained by treatment of dehydroabietic acid witht thionyl chloride or by any other suitable method. Similar methods may be used in preparing the acid bromide.
- Dehydroabietinal is particularly useful as an intermediate for production of other compounds such as by condensation with phenols, amines,
- the method of producing dehydroabietinal which comprises reducing the acid chloride of dehydroabietic acid with hydrogen in the presence of a noble metal catalyst.
- dehydroabietinal which comprises reducing the acid chloride of dehydroabietic acid with hydrogen in the presence of a catalyst comprising palladium supported on 'barium sulfate.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Description
Patented May 25, 1943 DEHYDROABIETINAL AND METHOD OF PRODUCING William P. Campbell, Newark, DeL, assignor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Application August 11, 1942, Serial No. 454,457
6 Claims.
This invention relates to a new composition of matter and .to a method for its production. More particularly, it relates to dehydroabietinal as a new composition of matter and to a method of production thereof.
Several derivatives of dehydroabietic acid have been described in the art. However, the aldehyde containing the hydrocarbon nucleus of dehydroabietic acid but having the carboxyl group replaced by the aldehyde group has not been prepared or described previously.
Now, in accordance with this invention, it has been discovered that dehydroabietinal, the aldehyde corresponding to dehydroabietic acid with substitution of the carboxyl group by the aldehyde group, may be prepared. Its method of preparation, in accordance with this invention, involves reduction of the acid halide such as the acid chloride or acid bromide formed from. dehydroabietic acid.
Dehydroabietinal is believed to have the following structural formula:
The following example illustrates the method of producing dehyd-roabietinal described in accordance with this invention:
Example Thirty two parts by Weight of the acid chloride formed from dehydroabietic acid were dissolved in 440 parts by weight of dry xylene. To this solution 20 parts by weight of 10% palladium on barium sulfate catalyst were added and the vessel containing the mixture flushed out with nitrogen. The solution was then heated to the boiling point and a stream of dry hydrogen passed through the vessel. The hydrogen was dried by passage through sulfuric acid prior to entry into the reaction vessel. The solution was stirred vigorously while passing in the hydrogen. The excess hydrogen as well as the hydrogen chloride formed during the reaction were passed into water and the hydrogen chloride titrated with normal sodium hydroxide solution so as to follow the progress of the reaction. After 24 minutes the reaction had gone to completion as determined by the hydrogen chloride evolved. The solution was then cooled and the reaction vessel flushed out with nitrogen. The reaction solution was then filtered to separate the catalyst and the filtrate steam-distilled, leaving the dehydroabietinal behind as a viscous liquid. The dehydroabietinal was converted to its semicarbazone by dissolving in methyl alcohol and adding 'suflicient semicarbazide hydrochloride and 12 parts of sodium bicarbonate dissolved in methanol. The solution of the semicarbazone resulting was concentrated and cooled to precipitate the semicarbazone. The first crop of crystals obtained amounted to 8.3 parts by weight and a second crop amounted to 38% of the theoretical. The melting point of the crystalline semicarbazone was 217 to 219 C.
While the above example illustrates the reduction of the acid chloride of dehydroabietic acid by means of a catalyst comprising palladium on barium sulfate, other catalysts for carrying out the reduction may also be used such as other noble metal hydrogenation catalysts. The catalyst employed must be sufficiently active to facilitate the replacement of the halogen of the acid halide by hydrogen but not so active as to further reduce the aldehyde group formed. Palladium supported on an inert base such as barium sulfate is particularly desirable.
In carrying out the reduction with the palladium-barium sulfate catalyst, a solution of the acid halide such as the acid chloride or acid bromide of dehydroabietic acid in a suitable solvent such as benzene, toluene, xylene, or purified petroleum fractions, will be employed. The temperature for carrying out the reduction may be varied to provide suitable reaction but preferably will be within the range of about 80 to about C. The time required for carrying out the reaction will be dependent on the particular catalyst used as well as on the particular temperature used.
The acid chloride of dehydroabietic acid useful in the production of dehydroabietinal in accordance with this invention may be obtained by treatment of dehydroabietic acid witht thionyl chloride or by any other suitable method. Similar methods may be used in preparing the acid bromide.
Dehydroabietinal is particularly useful as an intermediate for production of other compounds such as by condensation with phenols, amines,
which comprises reducing the acid chloride of dehydroabietic acid with hydrogen in the presence of a catalyst.
5. The method of producing dehydroabietinal which comprises reducing the acid chloride of dehydroabietic acid with hydrogen in the presence of a noble metal catalyst.
6. The method of producing dehydroabietinal which comprises reducing the acid chloride of dehydroabietic acid with hydrogen in the presence of a catalyst comprising palladium supported on 'barium sulfate.
WILLIAM P. CAMPBELL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US454457A US2319976A (en) | 1942-08-11 | 1942-08-11 | Dehydroabietinal and method of producing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US454457A US2319976A (en) | 1942-08-11 | 1942-08-11 | Dehydroabietinal and method of producing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2319976A true US2319976A (en) | 1943-05-25 |
Family
ID=23804679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US454457A Expired - Lifetime US2319976A (en) | 1942-08-11 | 1942-08-11 | Dehydroabietinal and method of producing |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2319976A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2494253A (en) * | 1946-11-22 | 1950-01-10 | Ciba Pharm Prod Inc | Hydrophenanthrene compounds and process of making same |
-
1942
- 1942-08-11 US US454457A patent/US2319976A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2494253A (en) * | 1946-11-22 | 1950-01-10 | Ciba Pharm Prod Inc | Hydrophenanthrene compounds and process of making same |
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